Non-magnetic monocomponent positive toner composition having superior transfer efficiency

ABSTRACT

The present invention relates to a non-magnetic mono-component toner composition, which comprises a) a non-magnetic toner particle comprising a binding resin comprising a binder resin and a copolymer of a cyclic olefin and an acyclic olefin polymerized in the presence of a metallocene catalyst and a cocatalyst, a colorant, and a charge-control agent; b) fine powder of an organic compound containing fluorine that is added to the surface of the non-magnetic toner particle; and c) hydrophobic silica having a specific surface area of 100 to 240 m 2 /g. The toner composition of the present invention has superior transfer efficiency and charging properties and thus can obtain a stable image, does not show deteriorated image density, and does not generate background contamination of non-image areas and off-set due to deterioration of fixing properties, even if copying or printing is conducted therewith for a long time use.

BACKGROUND OF THE INVENTION

(a) Field of the Invention

The present invention relates to a non-magnetic mono-component tonercomposition, and more particularly to a non-magnetic mono-componenttoner composition which has superior transfer efficiency and chargingproperties, and thus can obtain stable images, does not showdeteriorated image density, and does not generate backgroundcontamination of non-image areas and off-set due to deterioration offixing properties, even if copying or printing is conducted therewithfor a long time use.

(b) Description of the Related Art

Generally, according to conventional electrophotography methods, anelectrostatic latent image forms on the surface of a photosensitivemember using photoconductive materials, the latent image is developedusing a toner, and the toner image is transferred to a recording mediumsuch as paper to obtain a copy fixed by heat or pressure, as disclosedin U.S. Pat. No. 2,297,691, Japanese Laid-Open Patent Publication No.42-23910, Japanese Laid-Open Patent Publication No. 43-24748, etc.

Additionally, various development methods for developing electrostaticlatent images using a toner are also known. For example, U.S. Pat. No.2,874,063 discloses a magnetic brush development method, U.S. Pat. No.2,618,552 discloses a cascade development method, Japanese Laid-OpenPatent Publication No. 41-9475 discloses a development method using amono-component insulating toner, and U.S. Pat. No. 3,909,258 discloses adevelopment method using a mono-component conductive toner, and amongthe above, the dual-component magnetic brush development method and themono-component insulating toner development method are predominantlyused.

However, the electrophotography development method wherein aphotosensitive member is uniformly charged, an electrostatic latentimage forms by light exposure or laser beam, and a toner is supplied tothe electrostatic latent image to form a visual image, has a problem inthat ozone is generated from a charging apparatus. Particularly, takingenvironmental aspects into consideration, an organic photosensitivemember that is most widely used generally has a negative chargeproperty, and thus prevention of ozone generation during the chargingprocess is difficult.

In order to reduce ozone, a contact charging method has been suggestedwherein a conductive member such as a conductive brush, a conductiveelastic member roller, etc. is contacted with a photosensitive memberand voltage is applied. However, such contact charging method involves aproblem in terms of contamination of the conductive members. Since theconductive member is in contact with a photosensitive member, a toner,external additive for a toner, etc. that are attached to thephotosensitive member are in turn attached to the conductive member togenerate an irregular charging on the surface of the photosensitivemember.

In order to solve the above problems, an organic photosensitive memberhaving a positive charge property has been developed. If a positivecharge is used, even if a corona charging method is used, ozonegeneration can be reduced to approximately 1/10 compared to a negativecharge.

Meanwhile, a non-magnetic mono-component toner used in the positivecharging development method requires high transfer efficiency and highchargeability compared to the negative charging development method. Forthis, an external additive is attached to a toner particle. However, inthe case a toner to which one kind of external additive is attached isused for the non-magnetic mono-component development method, since thereis friction between the toner particle and a doctor blade or adeveloping roller, the external additive attached to the toner particlesurface is embedded in the toner particle, and thus theflowability-increasing effect of the external additive deteriorates, andtransfer efficiency and charging properties are not sufficient, therebydeteriorating the image after printing and the long term stability ofthe image.

In order to solve the above problems, a method has been suggestedwherein a toner with a positive charge property is developed onto asurface of a positively charged organic photosensitive member, the tonerthat is developed with high transfer efficiency is transferred to areporting medium such as paper, and fine powder of an organic compoundcontaining fluorine is used in addition to a single external additive ofhydrophobic silica in order to reduce image background contamination.However, this method involves a problem in that off-set is generated inthe fixing process.

Accordingly, there are increasing needs for a non-magneticmono-component toner that has superior transfer efficiency and chargingproperties, and does not generate background contamination of non-imageareas and off-set due to deterioration of fixing properties.

SUMMARY OF THE INVENTION

The present invention relates to a non-magnetic mono-component tonercomposition that has superior transfer efficiency and chargingproperties, and thus can obtain a stable image, does not showdeterioration of image density, and does not generate backgroundcontamination of non-image areas and off-set due to deterioration offixing properties, even if copying or printing is conducted therewithfor a long time use.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In order to solve the problems of the prior art, it is an object of thepresent invention to provide a non-magnetic mono-component tonercomposition that has superior transfer efficiency and chargingproperties, and thus can obtain a stable image, does not showdeterioration of image density, and does not generate backgroundcontamination of non-image areas and off-set due to deterioration offixing properties, even if copying or printing is conducted therewithfor a long time use.

In order to achieve the above object, the present invention provides anon-magnetic mono-component toner composition which comprises:

a) 100 parts by weight of a non-magnetic toner particle comprising

i) 100 parts by weight of a binding resin comprising 10 to 90 parts byweight of a copolymer of a cyclic olefin and an acyclic olefinpolymerized in the presence of a metallocene catalyst and a cocatalyst,and 100 parts by weight of a binder resin,

ii) 1 to 20 parts by weight of a colorant, and

iii) 0.2 to 6 parts by weight of a charge-control agent;

b) 0.05 to 2.0 parts by weight of fine powder of an organic compoundcontaining fluorine that is added to the surface of the non-magnetictoner particle; and

c) 0.5 to 2.0 parts by weight of hydrophobic silica having a specificsurface area of 100 to 240 m²/g.

The present invention will be explained in more detail.

The present inventors, while studying a non-magnetic mono-componenttoner that has superior transfer efficiency and charging properties, anddoes not generate background contamination of non-image areas andoff-set due to deterioration of fixing properties, prepared anon-magnetic mono-component toner by externally adding hydrophobicsilica having a specific surface area of 100 to 240 m²/g and fine powderof an organic compound containing fluorine to a non-magnetic tonerparticle surface which comprises a binding resin comprising a copolymerof a cyclic olefin and an acyclic olefin polymerized in the presence ofa metallocene catalyst and a cocatalyst, and a binder resin, a colorant,and a charge-control agent. As a result, it was identified that thetoner has superior transfer efficiency and charging properties and thuscan obtain a stable image, does not show deterioration of image density,and does not generate background contamination of non-image areas andoff-set due to deterioration of fixing properties, even if copying orprinting is conducted therewith for a long time use, and completed thepreset invention.

The non-magnetic mono-component toner composition of the presentinvention is characterized in that hydrophobic silica having a specificsurface area of 100 to 240 m²/g and a fine powder of an organic compoundcontaining fluorine are externally added to a non-magnetic tonerparticle surface which comprises a binding resin comprising a binderresin and a copolymer of a cyclic olefin and an acyclic olefinpolymerized in the presence of a metallocene catalyst and a cocatalyst,a colorant, and a charge-control agent.

The non-magnetic toner particle comprises 100 parts by weight of abinding resin comprising 100 parts by weight of a binder resin and 10 to90 parts by weight of a copolymer of a cyclic olefin and an acyclicolefin polymerized in the presence of a metallocene catalyst and acocatalyst, 1 to 20 parts by weight of a colorant, and 0.2 to 6 parts byweight of a charge control agent, on the basis of 100 parts by weight ofthe binding resin, and it may further comprise a release agent such aspolypropylene or polyethylene.

The copolymer of a cyclic olefin and an acyclic olefin is preferablycontained in 100 parts by weight of the binder resin in an amount of 10to 90 parts by weight. If the content is less than 10 parts by weight,it cannot solve off-set due to deterioration of fixing properties causedby an externally added fine powder of an organic compound containingfluorine, and if the content exceeds 90 parts by weight, compatibilitywith a binder resin decreases and thus dispersion between toneringredients is not uniform to deteriorate charging properties, and costof raw material increases as the used amount increases and thus it isnot economical.

The copolymer of a cyclic olefin and an acyclic olefin is prepared bycopolymerizing a cyclic olefin monomer with an acyclic monomer withoutopening a ring of the cyclic olefin monomer using a metallocene catalystand a cocatalyst. The copolymer preferably comprises at least 14 mol %of norbornene-type monomers, and more preferably at least 50 mol % ofnorbornene-type monomers.

As the cyclic monomer, a norbornene-type monomer represented by one ofthe following Chemical Formulae 1 to 6, or an ethylene-based cyclicmonomer represented by the following Chemical Formula 7 can be used:

In the above Chemical Formulae 1 to 6,

R¹ to R⁸ are independently hydrogen, C6-C16 aryls, or C1-C8 alkyls.

In the above Chemical Formula 7, n is an integer of 2 to 10.

The monocyclic olefin compound represented by the above Chemical Formula7 can be substituted with an aryl or alkyl radical. As the monocyclicolefin compound, cyclopentene, cycloindene, or cyclooctene can be used,and preferably cyclopentene is used.

The cyclic olefin monomer is preferably contained in an amount of 0.01to 99.9 wt %. If the content is less than 0.01 wt %, the resultingpolymer may become polyethylene, and if the content exceeds 99.9 wt %,the resulting polymer may become polynorbornene.

As the acyclic olefin monomer, a compound represented by the followingChemical Formula 8 is preferably used.

In the above Chemical Formula 8, R⁹ to R¹² are independently hydrogen,or C1-C8 alkyls.

The acyclic olefin monomer is preferably contained in an amount of 0.01to 99.9 wt %. If the content is less than 0.01 wt %, the resultingcopolymer may become polyethylene, and if the content exceeds 99.9 wt %,the copolymer may become polynorbornene.

The copolymer of the cyclic olefin and acyclic olefin is preferably acopolymer of a polycyclic olefin monomer represented by the aboveChemical Formula 1 or 2 and an acyclic olefin monomer represented by theabove Chemical Formula 8. And, polycyclic olefin derivatives comprisingnorbornene and tetracyclododecene and substituted with C1-C6 alkyl canalso be used, which can be copolymerized with ethylene.

The copolymer can be polymerized by a common method, and it ispreferably polymerized at 20˜120° C. under a pressure of 1-60 bar.

The polymerization of the copolymer is conducted in solution, and it ispreferable to polymerize in the presence of a metallocene catalyst and acocatalyst in order to facilitate polymerization of the desiredcopolymer. The cocatalyst is preferably contained in an amount of 1 wt %to saturation concentration, and the metallocene catalyst is preferablycontained in an amount of 10⁻⁴ to 10⁻² moles per 1 mole of thecocatalyst.

The metallocene catalyst can perform only in the presence of acocatalyst. If a cocatalyst is not used, polymerization of the copolymerof a cyclic olefin and an acyclic olefin progresses very slowly, andeven when 48 hours are passed, the copolymer may not be prepared. Thus,the polymerization should be conducted together with a cocatalyst.

It is preferable to previously mix the metallocene catalyst with acocatalyst to activate at a temperature of 15 to 70° C. for 15 to 60minutes, and introduce the mixture into a reactor.

The metallocene catalyst is preferably represented by the followingChemical Formula 9.

In the above Chemical Formula 9,

M¹ is titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium(Nb), or tantalum (Ta);

R¹⁴ and R¹⁵ are independently hydrogen, halogens, C1-C10 alkyls, C1-C10alkoxys, C6-C10 aryls, C6-C10 aryloxys, C2-C10 alkenyls, C7-C40arylalkyls, C7-C40 alkylaryls, or C8-C40 arylalkenyls; and R¹⁶ and R¹⁷are independently mononuclear or polynuclear hydrocarbon radicals, whichcan form a ring together with the center atom M1.

wherein to R¹⁹ to R²¹ are independently hydrogen, halogens, C1-C10alkyls, C1-C10 fluoroalkyls, C1-C10 fluoroaryls, C6-C10 aryls, C1-C10alkoxys, C6-C10 aryloxys, C2-C10 alkenyls, C7-C40 arylalkyls, orC8-C40 arylalkenyls; R¹⁹ to R²¹ may be independently connected toneighboring carbon atoms to form a ring; and M² is silicon (Si),germanium (Ge), or tin (Sn).

The metallocene catalyst is selected from the group consisting ofrac-ethylene-bis-(1-indenyl)-zirconium dichloride,isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride,rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride,rac-dimethylgermyl-bis-(1-indenyl)-zirconium dichloride,rac-phenylmethylsilyl-bis-(1-indenyl)-zirconium dichloride,rac-phenylvinylsilyl-bis-(1-indenyl)-zirconium dichloride,1-silacyclobutyl-bis-(1′-indenyl)-zirconium dichloride,rac-diphenylsilyl-bis-(1-indenyl)-halfnium dichloride,rac-phenylmethylsilyl-bis-(1-indenyl)-halfnium dichloride,rac-dimethylsilyl-bis-(1-indenyl)-halfnium dichloride,rac-diphenylsilyl-bis-(1-indenyl)-zirconium dichloride,diphenylmethylene-(9-flourenyl)-cyclopentandienyl-zirconium dichloride,and a mixture thereof. The metallocene catalyst can be used alone or incombination of two or more kinds.

The metallocene catalyst is preferably contained in an amount of 10⁻⁴ to10⁻⁶ moles per 1 L of reactor volume, based on the amount of transitionmetal. If the content is less than 10⁻⁶ moles, productivity decreases,and if the content exceeds 10⁻⁴ moles, highly viscose polymer isprepared, which is difficult to transfer.

The cocatalyst is preferably a linear aluminoxane represented by thefollowing Chemical Formula 10, or a cyclic aluminoxane represented bythe following Chemical Formula 11.

In the above Chemical Formulae 10 and 11,

R¹³ is independently a C1-C6 alkyl, a C1-C6 phenyl, or a C1-C6 benzyl,and n is an integer of 2 to 50.

The cocatalyst is preferably contained in an amount of 1 to 10⁻⁴ molesper 1 L of reactor volume, based on the amount of aluminum (Al). If thecontent exceeds 1 mole, post treatment cost increases due to anexcessively introduced amount, and if the content is less than 10⁻⁴moles, a catalyst cannot be activated.

After polymerization in the presence of the metallocene catalyst and thecocatalyst is completed, the copolymer of the cyclic olefin and theacyclic olefin is separated by introducing the polymerization productinto a filter media together with water to precipitate, filter, andremove remaining catalyst and cocatalyst in the polymerization product,and then introducing the polymerization product into an anti-solvent tocause phase separation, and filtering it to obtain a solid phasepolymer; or by recovering solvent and unreacted monomers with flashseparation using a thin film evaporator to obtain a solid phase polymer.

Thus a polycyclic bi-copolymer, a polycyclic tert-copolymer, or apolycyclic multi-copolymer, etc. can be obtained.

After polymerization, although the monomer incorporation ratio may bevaried according to polymerization factors such as reaction temperature,reaction pressure, catalyst concentration, cocatalyst concentration,etc., the incorporation ratio of cyclic olefin monomers is preferably 10to 80 mole %.

And, the average molecular weight of the obtained copolymer may bevaried according to degree of hydrogenation, change in catalystconcentration, temperature change, etc., and dispersity of the copolymer(Mw/Mn) is preferably 2.0 to 3.5. If the dispersity of the copolymer isless than 2.0, fixing is inferior, and if the dispersity exceeds 3.5,compatibility with the binder resin tends to decrease, and thusproperties required in the present invention are insufficient.

As the binder resin, a common fixing resin can be used. A compoundobtained by polymerization condensation of alcohol and carboxylic acidcan be used.

As the alcohol, a divalent or multivalent alcohol such as ethyleneglycol, diethylene glycol, triethylene glycol, polyethylene glycol,propylene glycol, butanediol, pentenediol, hexanediol,cyclohexanedimethanol, xylene glycol, bisphenol A, bisphenol A ethyleneoxide, bisphenol A propylene oxide, sorbitol, glycerin, etc., or alcoholderivatives can be used.

As the carboxylic acid, divalent or multivalent carboxylic acid such asmaleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalicacid, succinic acid, adipic acid, trimellitic acid, cyclopentenedicarboxylic acid, succinic acid anhydride, trimellitic acid anhydride,or maleic acid anhydride, etc., carboxylic acid derivatives, orcarboxylic acid anhydride can be used.

The binder resin obtained by polymerization condensation of the alcoholand the carboxylic acid includes: an acrylic acid ester polymer such aspolyester, polymethylacrylic acid, polyethylacrylic acid,polybutylacrylic acid, poly 2-ethylhexyl acrylic acid, or polylaurylacrylic acid, etc.; a methylacrylic acid ester polymer such aspolymethylmethacrylic acid, polybutylmethacrylic acid,polyhexylmethacrylic acid, poly 2-ethylhexyl methacrylic acid, orpolylauryl methacrylic acid, etc,.; a copolymer of an acrylic acid esterand a methacrylic acid ester; a copolymer of a styrene monomer and anacrylic acid ester or a methacrylic acid ester; an ethylene polymer suchas polyvinylacetic acid, polyvinylpropionic acid, polyvinyllactic acid,polyethylene, or polypropylene, etc. or a copolymer thereof; a styrenecopolymer such as a styrene-butadiene copolymer, a styrene-isoprenecopolymer, or a styrene-maleic acid copolymer, etc.; polyvinylether;polyvinyl ketone; polyester; polyamide; polyurethane; a rubber-likesubstance; an epoxy resin; a polyvinylbutyrol rosin; a modified rosin;and a phenol resin, etc. Preferably, polyester is used.

As the colorant, a black colorant such as carbon black and a coloredcolorant such as a yellow colorant, a magenta colorant, or a cyancolorant can be used.

The yellow colorant includes a condensed nitrogen compound, anisoindolinone compound, an anthraquine compound, an azo metal complex,and an allyl amide compound, etc. For example, C.l.pigment yellow 12,C.l.pigment yellow 13, C.l.pigment yellow 14, C.l.pigment yellow 15,C.l.pigment yellow 17, C.l.pigment yellow 62, C.l.pigment yellow 74,C.l.pigment yellow 83, C.l.pigment yellow 93, C.l.pigment yellow 94,C.l.pigment yellow 95, C.l.pigment yellow 109, C.l.pigment yellow 110,C.l.pigment yellow 111, C.l.pigment yellow 128, C.l.pigment yellow 129,C.l.pigment yellow 147, or C.l.pigment yellow 168 can be used.

The magenta colorant includes condensed a nitrogen compound,anthraquine, a quinacridone compound, a base dye lake compound, anaphthol compound, a benzoimidazole compound, a thioindigo compound, anda pherylene compound, etc. For example, C.l.pigment red 2, C.l.pigmentred 3, C.l.pigment red 5, C.l.pigment red 6, C.l.pigment red 7,C.l.pigment red 23, C.l.pigment red 48:2, C.l.pigment red 48:3,C.l.pigment red 48:4, C.l.pigment red 57:1, C.l.pigment red 81:1,C.l.pigment red 144, C.l.pigment red 146, C.l.pigment red 166,C.l.pigment red 169, C.l.pigment red 177, C.l.pigment red 184,C.l.pigment red 185, C.l.pigment red 202, C.l.pigment red 206,C.l.pigment red 220, C.l.pigment red 221, or C.l.pigment red 254 can beused.

The cyan colorant includes a copper phthalocyanine compound andderivative thereof, an anthraquine compound, and a base dye lakecompound, etc. For example, C.I.pigment blue 1, C.I.pigment blue 7,C.I.pigment blue 15, C.I.pigment blue 15:1, C.I.pigment blue 15:2,C.I.pigment blue 15:3, C.I.pigment blue 15:4, C.I.pigment blue 60,C.I.pigment blue 62, or C.I.pigment blue 66 can be used.

The colorant is preferably contained in a sufficient amount to form avisual phase of sufficient concentration, and generally it is containedin an amount of 1 to 20 parts by weight, based on 100 parts by weight ofthe binding resin.

As the charge-control agent, a diallyl alkyl ammonium salt polymer or anigrosine dye can be used.

The charge-control agent is preferably contained in an amount of 0.2 to6 parts by weight, based on 100 parts by weight of the binding resin. Ifthe content is less than 0.2 parts by weight, image density is notsufficient, and if the content exceeds 6 parts by weight, the effectincrease is little, and production cost increases.

The toner particle is prepared by common pulverization through meltblending or polymerization, and the average particle diameter of theprepared toner particle is, although not limited, preferably 5 to 30 μm.

The present invention is characterized by externally adding hydrophobicsilica having specific surface area of 100 to 240 m²/g and fine powderof an organic compound containing fluorine to the surface of the tonerparticle.

As the organic compound containing fluorine, polyfluorovinylidene orpolytetrafluoroethylene can be used, and preferablypolytetrafluorethylene is used.

The average particle diameter of the fine powder of the organic compoundcontaining fluorine is preferably 0.1 to 4.0 μm, and more preferably 0.2to 2.0 μm. If the diameter is less than 0.1 μm, the diameter of the finepowder is too small and the powder is completely embedded in the tonerby operation of a high-speed mixer. Thus, the effects of decreasingfriction between the charge-providing member and preventingcontamination decrease and thus long term stability is not maintained.And, if the particle diameter exceeds 4.0 μm, the mixing property withthe non-magnetic toner is insufficient and thus the particles are likelyto disperse at the surface of the development roller, and thecharge-providing member of the charging apparatus is contaminated todeteriorate image density.

The fine powder of the organic compound containing fluorine ispreferably contained in an amount of 0.05 to 2.0 parts by weight, basedon 100 parts by weight of toner particle, and more preferably in anamount of 0.1 to 1.5 parts by weight. If the content is less than 0.05parts by weight, the toner particle surface is not sufficiently coatedwith the fine powder and thus the toner cannot be sufficientlypositively charged, and toner durability and developer performancedeteriorate due to sticking of the toner particle to the chargeproviding member. And, if the content exceeds 2.0 parts by weight,durability of the toner decreases because of sticking to thecharge-providing member due to exfoliation of the added powder, and thefixing property deteriorates even if a copolymer of a cyclic olefin andan acyclic olefin is used together, due to complete coating of the tonerparticle with fine powder.

The hydrophobic silica having a specific surface area of 100 to 240 m²/gimproves flowability and charging properties of the toner particle.

The specific surface area of the hydrophobic silica is preferably 100 to240 m²/g, and more preferably 130 to 200 m²/g. If the specific surfacearea is less than 100 m²/g, the flowability improvement effect is notsufficient and thus image contamination such as staining on a solidimage may occur. And, if the specific surface area exceeds 240 m²/g,silica is embedded onto the surface of the toner particle and thus theflowability improvement effect decreases, which decreases the effects ofthe fine powder.

The hydrophobic silica is preferably contained in an amount of 0.5 to2.0 parts by weight, based on 100 parts by weight of the toner particle.If the content is less than 0.5 parts by weight, the flowabilityimprovement effect is not sufficient, and if the content exceeds 2.0parts by weight, the hydrophobic silica sticks to the surface of thetoner particle, and the fixing property decreases.

The hydrophobic silica is prepared by making silica particleshydrophobic, preferably by coating or attaching an aminosilane-typecoupling agent that contains positive charges on silica particles.

As the positive charge-containing aminosilane-type coupling agent,H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃, H₂N(CH₂)₂NH(CH₂)₃Si(CH₃)(OCH₃)₂,H₂N(CH₂)₂NH(CH₂)₂Si(OCH₃)₃, H₂N(CH₂)₂NH(CH₂)₂NH(CH₂)₂Si(OCH₃)₃,H₂N(CH₂)₃Si (OCH₃)₃, or C₆H₅NH(CH₂)₃Si(OCH₃)₃ can be used.

The fine powder of the organic compound containing fluorine andhydrophobic silica can be attached to the toner particle using a commonagitator such as a turbine type agitator, a Hensel type mixer, asupermixer, etc., or by using a surface modifying machine (Narahybridization system, Nara machine manufacture company). And, thehydrophobic silica may be weakly attached to the toner particle surface,or fixed on the surface with a part thereof embedded.

According to the non-magnetic mono-component toner of the presentinvention in which a fine powder of an organic compound containingfluorine is externally added to a toner particle comprising a copolymerof a cyclic olefin and an acyclic olefin, since the organic compoundpowder is selectively coated on the surface of the development rollerand the powder makes the surface strongly positive, when a positivephotosensitive member is used, the powder strongly pushes positive tonerto the organic photosensitive member surface thereby achieving hightransfer efficiency, and when transferred from a drum to a reportingmedium of paper, toner transfer efficiency also increases by the samereason. Therefore, a stable image can be obtained due to high transferefficiency, image density does not deteriorate, and backgroundcontamination of non-image areas is not caused. Also, off-setcontamination of fixing area caused when using conventional an organiccompound containing fluorine powder can be solved using the copolymer ofa cyclic olefin and an acyclic olefin.

Accordingly, the non-magnetic mono-component toner of the presentinvention has superior transfer efficiency and charging properties, andthus can obtain a stable image, the image density does not deteriorate,and background contamination of non-image areas and off-set due todeterioration of fixing properties are not generated, even if copying orprinting therewith is conducted for a long time use.

EXAMPLE Example 1

(Preparation of a Copolymer of a Cyclic Olefin and an Acyclic Olefin)

A clean and completely dried 100 mL batch type reactor was preparedunder an argon atmosphere, and then 800 mL of a norbornene solution (55wt %) dissolved in toluene was introduced therein and temperature waselevated to 70° C. Into the reactor,isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride as acatalyst and MMAO-4 as a cocatalyst were introduced, and thenpolymerization was conducted for 20 minutes while maintaining ethylenepressure of 70 psi. The ethylene was then vented, 3 mL of ethanol wasintroduced to stop polymerization, and the polymer solution was removedfrom the reactor, and 5 L of acetone was added to obtain a solid phasecopolymer. The obtained solid phase copolymer was filtered and thendried at 80° C. under reduced pressure for 18 hours to prepare acopolymer of a cyclic olefin and an acyclic olefin.

(Preparation of Toner Particle)

100 parts by weight of a polyester resin, 50 parts by weight of theprepared copolymer of a cyclic olefin and an acyclic olefin, 8 parts byweight of carbon black with an average particle diameter of 0.3 μm, 3parts by weight of nigrosine dye, and 5 parts by weight of a releaseagent (polypropylene wax) were mixed using a Hensel mixer. The mixturewas fusion blended in a twin screw extruder, mechanically pulverized,and distributed as 9.0 to 9.2 μm in a jet milling machine to preparetoner particle particles.

(Preparation of Non-Magnetic Mono-Component Toner)

To 100 parts by weight of the prepared toner particle, 0.05 parts byweight of polytetrafluorethylene fine powder and 1.0 parts by weight ofhydrophobic silica RA200HS with a positive charge property (JapanAerogel Company) were added, and they were agitated and mixed using aHensel mixer for 4 minutes to coat on the toner particle surface toprepare a non-magnetic mono-component toner.

Example 2

A non-magnetic mono-component toner was prepared by the same method asin Example 1, except that 1.0 parts by weight of polytetrafluorethylenefine powder were used.

Example 3

A non-magnetic mono-component toner was prepared by the same method asin Example 1, except that 20 parts by weight of polytetrafluorethylenefine powder were used.

Comparative Example 1

A non-magnetic mono-component toner was prepared by the same method asin Example 1, except that polytetrafluorethylene fine powder was notused.

Comparative Example 2

(Preparation of Toner Particle)

150 parts by weight of a polyester resin, 8 parts by weight of carbonblack with an average particle diameter of 0.3 μm, 3 parts by weight ofnigrosine dye, and 5 parts by weight of a release agent (polypropylenewax) were mixed using a Hensel mixer. The mixture was fusion blended ina twin screw extruder, mechanically pulverized, and then distributed as9.0 to 9.2 μm in a jet milling machine to prepare toner particleparticles.

(Preparation of Non-Magnetic Mono-Component Toner)

To 100 parts by weight of the prepared toner particle, 1.0 parts byweight of polytetrafluorethylene fine powder and 1.0 parts by weight ofhydrophobic silica RA200HS with a positive charge property (JapanAerogel Company) were added, and they were mixed and agitated using aHensel mixer for 4 minutes to coat on the toner particle surface toprepare a non-magnetic mono-component toner.

Comparative Example 3

A non-magnetic mono-component toner was prepared by the same method asin Example 1, except that 3.0 parts by weight of polytetrafluorethylenefine powder were used.

Comparative Example 4

A non-magnetic mono-component toner was prepared by the same method asin Example 1, except that 0.03 parts by weight of polytetrafluorethylenefine powder were used.

Experiment 1

8000 sheets at room temperature was printed with a commerciallyavailable non-magnetic mono-component development-type printer using thenon-magnetic mono-component toner prepared in Examples 1 to 3 andComparative Examples 1 to 4 as a contact development apparatus. And,image density, contamination of non-image areas, and fixing propertywere measured by the following methods, and the results are shown inTable 1.

a) image density (I.D.)—Image density of black solid area was measuredwith a densitometer (Mcbeth Company). If solid area image density is1.35 or more, the toner can be used.

b) non-image area contamination—measured with a densitometer, and thencompared with the value of reflection density of new paper. When thereis non-image area contamination, it is indicated as O, and when there isno contamination, it is indicated as X.

c) fixing property—judged according to whether or not the same lettersor patterns are repeated by off-set on an image printed at roomtemperature using a commercially available non-magnetic mono-componentdevelopment-type printer using non-magnetic mono-component toner ascontact development apparatus. In case repetition or image contaminationdue to off-set is not generated, it is judged as good, and in case it isgenerated, it is judged as no good (deterioration).

TABLE 1 Example Comparative Example 1 2 3 1 2 3 4 Image density (500sheets) 1.43 1.45 1.44 1.22 1.41 1.47 1.32 Image density (8000 sheets)1.41 1.42 1.41 1.14 1.39 1.23 1.30 Non-image area Contamination X X X ◯X X ◯ contamination Difference in 0.12 0.08 0.05 1.05 0.32 0.27 0.64reflection density Fixing property good good good good no good no goodgood

As shown in Table 1, the non-magnetic mono-component toners withpositive charging properties for developing electrostatic charge imagesaccording to Examples 1 to 3 of the present invention do not involveproblems in terms of image density, non-image part contamination, andfixing property, even if 8000 sheets is printed under common conditions.Specifically, the toner of the present invention has superior transferefficiency and thus can obtain a stable image, does not show imagedensity deterioration, has a superior fixing property, and does notgenerate background contamination of non-image areas, even if printingis conducted therewith for a long time use.

The non-magnetic mono-component toners with positive charging propertiesof Comparative Examples 1 to 4 began to show non-image areacontamination after printing 1000 sheets, and after printing 4000 sheetsthe image density deteriorated or the fixing area was contaminated.

As explained, the non-magnetic mono-component toner of the presentinvention has superior transfer efficiency and charging properties, andthus can obtain stable images, does not show a deteriorated imagedensity, and background contamination of non-image areas and off-set dueto deterioration of fixing properties are not generated, even if copyingor printing is conducted therewith for a long time use.

1. A non-magnetic mono-component toner composition which comprises: a)100 parts by weight of a non-magnetic toner particle comprising i) 100parts by weight of a binding resin comprising 10 to 90 parts by weightof a copolymer of a cyclic olefin and an acyclic olefin polymerized inthe presence of a metallocene catalyst and a cocatalyst, and 100 partsby weight of a binder resin, wherein the copolymer of a cyclic olefinand an acyclic olefin comprises at least 14 mol % of norbornene-typemonomers, ii) 1 to 20 parts by weight of a colorant, and iii) 0.2 to 6parts by weight of a charge-control agent; b) 0.05 to 2.0 parts byweight of fine powder of an organic compound containing fluorine whichis added to the surface of the non-magnetic toner particle, wherein theorganic compound containing fluorine is polyfluorovinylidene orpolytetrafluoroethylene and the fine powder of an organic compoundcontaining fluorine has an average particle diameter of 0.1 to 4.0 μm;and c) 0.5 to 2.0 parts by weight of hydrophobic silica having aspecific surface area of 100 to 240 m²/g, wherein the hydrophobic silicais prepared by making silica particles hydrophobic with anaminosilane-type coupling agent that contains a positively charged groupselected from the group consisting of H₂N(CH₂)₂NH(CH₂)₃Si(OCH₃)₃,H₂N(CH₂)₂NH(CH₂)₃Si(CH₃)(OCH₃)₂, H₂N(CH₂)₂NH(CH₂)₂Si(OCH₃)₃,H₂N(CH₂)₂NH(CH₂)₂NH(CH₂)₂Si(OCH₃)₃, H₂N(CH₂)₃Si (OCH₃₎ ₃,C₆H₅NH(CH₂)₃Si(OCH₃)₃, and a mixture thereof.
 2. The non-magneticmono-component toner composition according to claim 1, wherein the a) i)copolymer of a cyclic olefin and an acyclic olefin comprises 0.01 to99.9 wt % of cyclic olefin monomers and 0.01 to 99.9 wt % of acyclicolefin monomers.
 3. The non-magnetic mono-component toner compositionaccording to claim 2, wherein the cyclic olefin monomer is anorbornene-type monomer represented by one of the following ChemicalFormulae 1 to 6, or an ethylene-based monomer represented by thefollowing Chemical Formula 7:

wherein in the above Chemical Formulae 1 to 6, R¹ to R⁸ areindependently hydrogen, C6-C16 aryls, or C6˜C8 alkyls;

wherein in the above Chemical Formula 7, n is an integer of 2 to
 10. 4.The non-magnetic mono-component toner composition according to claim 2,wherein the acyclic olefin monomer is represented by the followingChemical Formula 8:

wherein in the above Chemical Formula 8, R⁹ to R¹² are independentlyhydrogen or C1-C8 alkyls.
 5. The non-magnetic mono-component tonercomposition according to claim 1, wherein the metallocene catalyst isrepresented by the following Chemical Formula 9:

wherein in the above Chemical Formula 9, M₁ is titanium (Ti), zirconium(Zr), hafnium (Hf), vanadium (V), niobium (Nb) or tantalum (Ta); R¹⁴ andR¹⁵ are independently hydrogen, halogens, C1-C10 alkyls, C1-C10 alkoxys,C6-C10 aryls, C6-C10 aryloxys, C2-C10 alkenyls, C7-C40 arylalkyls,C7-C40 alkylaryls, or C8-C40 arylalkenyls; R¹⁶ and R¹⁷ are independentlya mononuclear or polynuclear hydrocarbon radical that can form asandwich structure together with the center atom M^(1;) and

wherein R¹⁹ to R²¹ are independently hydrogen, halogens, C1-C10fluoroalkyls, C1-C10 fluoroaryls, C6-C10 aryls, C1-C10 alkoxys, C6-C10aryloxys, C2-C10 alkenyl, C7-C40 arylalkyls, or C8-C40 arylalkenyls, andR¹⁹ to R²¹ can be independently connected to neighboring carbons to forma ring; and M² is silicon (Si), germanium (Ge), or tin (Sn).
 6. Thenon-magnetic mono-component toner composition according to claim 1,wherein the metallocene catalyst is selected from the group consistingof rac-ethylene-bis-(1-indenyl)-zirconium dichloride,isopropylene-(9-fluorenyl)-cyclopentadienyl-zirconium dichloride,rac-dimethylsilyl-bis-(1-indenyl)-zirconium dichloride,rac-dimethylgermyl-bis-(1-indenyl)-zirconium dichloride,rac-phenylmethylsilyl-bis-(1-indenyl)-zirconium dichloride,rac-phenylvinylsilyl-bis-(1-indenyl)-zirconium dichloride,1-silacyclobutyl-bis-(1 ′-indenyl)-zirconium dichloride,rac-diphenylsilyl-bis-(1-indenyl)-halfnium dichloride,rac-phenylmethylsilyl-bis-(1-indenyl)-halfnium dichloride,rac-dimethylsilyl-bis-(1-indenyl)-halfnium dichloride,rac-diphenylsilyl-bis-(1-indenyl)-zirconium dichloride, anddiphenylmethylene-(9-flourenyl)-cyclopentandienyl-zirconium di chloride.7. The non-magnetic mono-component toner composition according to claim1, wherein the cocatalyst is a linear aluminoxane represented by thefollowing Chemical Formula 10, or a cyclic aluminoxane represented bythe following Chemical Formula 11:

wherein in the above Chemical Formulae 10 and 11, R¹³ is independently aC1-C6 alkyl, a C1-C6 phenyl, or a C1-C6 benzyl, and n is an integer of 2to
 50. 8. The non-magnetic mono-component toner composition according toclaim 1, wherein the copolymer of a cyclic olefin and an acyclic olefinhas dispersity of 2.0 to 3.5.
 9. The non-magnetic mono-component tonercomposition according to claim 1, wherein the binder resin is preparedby condensation polymerization of alcohol and carboxylic acid.
 10. Thenon-magnetic mono-component toner composition according to claim 9,wherein the alcohol is selected from the group consisting of ethyleneglycol, diethylene glycol, triethylene glycol, polyethylene glycol,propylene glycol, butanediol, pentenediol, hexanediol,cyclohexanedimethanol, xylene glycol, bisphenol A, bisphenol A ethyleneoxide, bisphenol A propylene oxide, sorbitol, glycerin, and derivativesthereof.
 11. The non-magnetic mono-component toner composition accordingto claim 9, wherein the carboxylic acid is selected from the groupconsisting of maleic acid, fumaric acid, phthalic acid, isophthalicacid, terephthalic acid, succinic acid, adipic acid, trimellitic acid,cyclopentene dicarboxylic acid, succinic acid anhydride, trimelliticacid anhydride, maleic acid anhydride, carboxylic acid derivative,carboxylic acid anhydride, and a mixture thereof.
 12. The non-magneticmono-component toner composition according to claim 1, wherein thebinder resin is selected from the group consisting of polyester,polymethylacrylic acid, polyethylacrylic acid, polybutylacrylic acid,poly 2-ethylhexyl acrylic acid, polylauryl acrylic acid,polymethylmethacrylic acid, polybutylmethacrylic acid,polyhexylmethacrylic acid, poly 2-ethylhexyl methacrylic acid,polylauryl methacrylic acid, a copolymer of an acrylic acid ester and amethacrylic acid ester, a copolymer of a styrene monomer and an acrylicacid ester or a methacrylic acid ester, polyvinylacetic acid,polyvinylpropionic acid, polyvinyllactic acid, polyethylene,polypropylene, a styrene-butadiene copolymer, a styrene-isoprenecopolymer, a styrene-maleic acid copolymer, polyvinyl ether, polyvinylketone, polyester, a polyamide, polyurethane, rubber, an epoxy resin, apolyvinylbutyrol rosin, a modified rosin, a phenol resin, and a mixturethereof.
 13. The non-magnetic mono-component toner composition accordingto claim 1, wherein the colorant is selected from the group consistingof carbon black, C.l. pigment yellow 12, C.l. pigment yellow 13, C.l.pigment yellow 14,C.l. pigment yellow 15, C.l. pigment yellow 17, C.l.pigment yellow 62, C.l. pigment yellow 74, C.l. pigment yellow 83, C.l.pigment yellow 93, C.l. pigment yellow 94, C.l. pigment yellow 95, C.l.pigment yellow 109, C.l. pigment yellow 110, C.l. pigment yellow 111,C.l. pigment yellow 128, C.l. pigment yellow 129, C.l. pigment yellow147, C.l. pigment yellow 168, C.l. pigment red 2, C.l. pigment red 3,C.l. pigment red 5, C.l. pigment red 6, C.l. pigment red 7, C.l. pigmentred 23, C.l. pigment red 48:2, C.l. pigment red 48:3, C.l. pigment red48:4, C.l. pigment red 57:1, C.l. pigment red 81:1, C.l. pigment red144, C.l. pigment red 146, C.l. pigment red 166, C.l. pigment red 169,C.l. pigment red 177, C.l. pigment red 184, C.l. pigment red 185, C.l.pigment red 202, C.l. pigment red 206, C.l. pigment red 220, C.l.pigment red 221, C.l. pigment. red 254, C.l. pigment blue 1, C.l.pigment blue 7, C.l. pigment blue 15, C.l. pigment blue 15:1, C.l.pigment blue 15:2, C.l. pigment blue 15:3, C.l. pigment blue 15:4, C.l.pigment blue 60, C.l. pigment blue 62, and C.l. pigment blue
 66. 14. Thenon-magnetic mono-component toner composition according to claim 1,wherein the charge-control agent is a diallyl alkyl ammonium saltpolymer or a nigrosine-type pigment.
 15. The non-magnetic mono-componenttoner composition according to claim 1, wherein the a) toner particlehas an average particle diameter of 5 to 30 μm.